A process of milling fungi with acetylenic ketones

ABSTRACT

Compounds of the formula WHERE R1 is ethyl or phenyl and R2 is lower alkyl are useful as fungicides. The compound 3-heptyn-5-one is particularly valuable since it is not toxic to plants.

United States Patent Gier et al.

[54] PROCESS OF MILLING FUNGI WITH ACETYLENIC KETONES [72] Inventors: Delta W. Gier; Audra M. Calhoon,

both of Albert Lea, Minn. [73] Assignee: Chemagro Corporation, New York,

22 Filed: May26, 1970 211 Appl.No.: 40,712

Related us. Application Data [62] Division of Ser. No. 761,965, July- 16, 1968, Pat. No. 3,592,922, which is a division of Ser.

No. 675,318, Oct. 16, 1967, abandoned.

[52] US. Cl ..424/331 [51] Int. Cl. ..A01n 9/24 [58] Field of Search ..42 4/331 Reisch et al. Chem. Abst. Vol. 67 (1967) page 88434m Primary Examinen-Sam Rcsen Attorney-Cushman, Darby & Cushman [57] ABSTRACT I Compounds of the formula 0 R1C EQ(|R2 where R is ethyl or phenyl and R 'is lower alkyl are useful as fungicides. The compound 3-heptyn-5-one is particularly valuablesince it is not toxic to plants.

8 Claims, No Drawings A PROCESS OF MILLING FUNGI WITH ACETYLENIC KETONES The present application is a divisional application of Ser. No. 761,965 filed July 16, 1968 now U.S. Pat. No. 3,592,922 which in turn is a division of application Ser. No. 675,318 filed Oct. 16, 1967 and now abandoned.

The present invention relates to fungicides.

Youngson U.S. Pat. No. 2,905,588 discloses the use of ethynyl ketones of the formula RC 5 CH where R is an acyl radical as nematocides and fungicides. These compounds are all characterized by having a hydrogen atom attached to one of the acetylenic carbon atoms. Youngson also requires the use of the relatively dangerous acetylene and the relatively expensive Grignard reagents to make his products.

An object is to prepare novel fungicides.

A further object is to develop fungicides which are not injurious to crops.

Still further objects and the entire scope of applicability of the present invention will, become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained by preparing alpha acetylenic ketones of the formula and applying them to fungi. In the formula R is ethyl or In place of water there can be employed organic solvents as carriers, e.g., hydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil, fuel oil, and petroleum naphtha, ketones such as acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbon tetra-chloride, chloroform, trichloroethylene and perchloroethylene, esters such as ethyl acetate, amyl acetate and butyl acetate, ethers, e.g., ethylene glycol monomethyl ether and diethylene glycol monoethyl ether, alcohols, e.g. ethanol, methanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, butyl carbitol acetate and glycerine. Mixtures of water and organic solvents, either as solutions or emulsions, can be employed.

The pesticides of the present invention can also be applied with fungicidal adjuvants or carriers such as tale, pyrophyllite, synthetic fine silica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, benotonite, Fullers earth,,cottonseed hulls, wheat flour, soybean flour, pumice, tripoli, wood flour, walnut shell flour, redwood flour and lignin. It is frequently desirable to incorporate a surface active agent in-the pesticidal compositions of the present invention. Such surface active or wetting agents are advantageously-employed in both the solid and liquid compositions. The surface active agent can be anionic, cationic or nonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts, alkylaryl sulfonate salts, alkyl sulfate salts, alkylamide sulfonate salts, alkylaryl polyether alcohols, fatty acid esters of polyhydric alcohols and the alkylene oxide addition products of such esters, and adphenyl while R is lower alkyl. Such products do not i have significant herbicidal activity and hence can be safely used to protect crops from fungi.

Examples of compounds useful within the invention are 3-heptyn -5-one, 3-hexyne-5-one, 6-methyl- 3-heptyn-S-one, 3-octyn-5-one, 3-nonyn-5-one, l-butyn-3- one-l-phenyl, l-pentyn-S-one-l-phenyl, l-pentyn-3- one-4-methyl-l-phenyl, l-hexyn-3-one-l-phenyl, lheptyn-3-one-l-phenyl. 1

The alpha acetylenic ketones are prepared by reacting ethyl acetylene or phenyl acetylene with sodium or potassium or a sodium-potassium alloy and reacting the resulting alkali metal ethyl (or phenyl) acetylide with the appropriate acyl halide, e.g. acetyl chloride, acetyl bromide, propionyl chloride, propionyl bromide, butyryl chloride, isobutyryl chloride, valeryl chloride.

The compounds of the present invention can be used alone as fungicides but it has been found desirable to apply them to the habitat of the fungi together with inert solids to form dusts or, more preferably, suspended in a suitable liquid diluent, preferably water. They can be applied at widely varying rates, e.g. 0. l-30 lbs/acre.

There can also be added surface active agents or wetting agents and inert solids in such liquid formulations. Desirably, 0.05l percent by weight of. surface active or wetting agent is employed. The active ingredient can be from 0.01 to 95 percent by weight of the entire composition in such case.

dition products of long chain mercaptans and alkylene oxides. Typical examples of such surface active agents include the sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in the alkyl group, alkylphenol ethylene oxide condensation products, e.g., p-isooctylphenol condensed with 10 ethylene oxide units, soaps, e.g., sodium stearate and potassium oleate, sodium salt of propylnaphthalene sulfonic acid, (di-2-ethylhexyl) ester of sodium sulfosuccinic acid, sodium lauryl sulfate, sodium salt of the sulfonated monoglyceride of cocoanut fatty acids, sorbitan sesquioleate, lauryl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, polyethylene glycol lauryl ether,

polyethylene esters of fatty acids and rosin acids, e.g.,-

Ethofat 7 and 13, sodium N-methyl-N-oleyltaurate, Turkey Red Oil, sodium dibutylnaphthalene sulfonate, sodium lignin sulfonate (Marasperse N), polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiary. dodecyl polyethylene glycol thioether (Nonionic 218), long chain ethylene oxide-propylene oxide condensation products, e.g., Pluronic 61 (molecular weight 1,000), sorbitan sesquioleate, polyethylene glycol ester of tall oil acids, sodium octyl phenoxyethoxyethyl sulfate, tris (polyoxyethylene) sorbitan monostearate (Tween 60), sodium dihexyl sulfosuccinate.

The solid and liquid formations can be prepared by any of the conventional procedures. Thus, the active ingredients can bemixed with the solid carrier in finely divided form in amounts small enough to preserve the free-flowing property of the final dust composition.

Unless otherwise indicated all parts and percentages are by weight.

EXAMPLE 1 The following general method was employed in preparing the alpha-acetylenic ketones. A 500 ml. three-neck flask equipped with a mechanical stirrer, a dry ice condenser and a gas inlet tube was charged with 300 ml. of *dry tetrahydrofuran and the system was swept with dry nitrogen. Sodium-potassium alloy (0.15 mole) was addedunder a nitrogen atmosphere. The gas inlet tubewas replaced with a dropping funnel containing. about percent excess butyne-l or phenylacetylenein 50 ml. ofdry tetrahydro'furan. The butyne-l or phenylacetylene was added 'dropwise with vigorous stirring and intermittent dry ice cooling to prevent overheating (the temperature was held below 50 C.). The reaction mixture immediately turned a deep purple and gradually changed to light gray as the reaction approached completion.

When no more free metal appeared visible, the reaction mixture was chilled in a dry ice-acetone bath and a stoichiometric amount (based on the sodium-potassium alloy used) of the appropriate acid chloride (e.g. propionyl chloride to prepare compound .1) in 50 ml. of dry tetrahydrofuran was added dropwise at dry ice temperature. The mixture was allowed to slowly attain room temperature and was continually stirred for an additional 2 hours.-The slurry was then added cautiously to 1 liter of water and crushed ice. The nonaqueous layer .was separated, washed with 10 percent aqueous sodium carbonate solution, washed again with water and then dried over calcium sulfate. The trapped solvent was removed by distillation under vacuum and the crude product purified. The liquid ketones formed were purified by vacuum distillation. The solid ketones formed were purified by recrystallization from ethanol or ethanol-water mixtures.

The alpha acetylenic ketones formed are set forth in Table l and had the formula The compounds were tested as fungicides in Agar plate tests and insoil fungicide tests. In the Agar plate tests recorded in Table 2 the compound was added to Agar containing the following fungi Colletotrichum obiculare, Rhizoctonia solani, Fusarium lycopersici,

l-lelminthospo'rium sativum and Verticillium alboatrum.

In Table 2, Rate A is 1,000 ppm, Rate B is ppm, and Rate C is 10 ppm. The results are recorded on a 0 to 10 scale where 0 indicates no inhibition'of growth and 10 indicates perfect inhibition of growth.

In the soil fungicide tests which are recorded in Table 3 the compounds were added as F orrnulationA to soil planted with pea seedlings and infested with Pythium spp. The results were recorded at rates of 200 ppm. and 50 ppm. and on a 0 to 10 scale wherein 0 indicates no inhibition and 10 indicates complete inhibition.

TABLE2 Comcollectohelminth- Rhiz- Vertipound rate trichum Fusarium osporiurn octonia cillium 1 A 10 10 10 l0 10 B l0 l0 I0 10 10 C l0 l0 l0 l0 l0 4 A 0 0 0 0 10 B 0 0 0- 0 0 C 0 O 0 0 0 5 A 0 0 0 0 0 B 0 0' '0 0 O C 0 O I 0 0 0 8 A l0 l0 l0 l0 l0 B 0 5 5 l0 5 C 0 0 0 0 0 9 A 8 l0 l0 B 5 5 8 C 0 O 5 10 A 10 l0 l0 l0 10 B l0 l0 l0 l0 10 C 10 8 8 l0 5 ll A l0 l0 l0 l0 10 B 10 l0 l0 10 10 C l0 l0 l0 10 10 12 A 10 10 B 10 10 C 5 5 13 A l0 l0 l0 I0 10' B l0 l0 10 10 8 C 5 5 l0 l0 5 14 A 5 5 5 5 0 B 0 5 5 0 0 C 0 0 0 0 0 TABLE 3 Compound Rate Activity 50 2 10 200 9 50 9 ll 200 10 50 9 12 200 9 S0 4 13 200 9 5O 4 14 200 4 4 It will be observed fromTables 2 and 3 that the higher alkyl Compound 5 (R is tridecyl) did not show any significant fungicidal activity and the activity of Compound 4 (R, is allyl) was minor.

herbicides at the indicated dosages in lbs/acre. The results are set forth in Table 4.

A to 10 scale was employed wherein 0 indicates no effect and indicates 100 percent kill of the plants.

TABLE 4 Com- Sugar pound Rate Oats Beets Radish Flax Wheat 1 8 0 0 0 0 0 2 0 0 0 0 0 8 8 7 l0 9 l0 4 2 7 l0 9 l0 6 9 8 2 8 8 8 l 2 0. 7 8 7 2 10 8 4 9 7 8 2 2 0 0 l l 0 ll 8 3 9 4 7 5 2 0 5 4 3 2 l2 8 3 9 6 4 5 2 a O 3 3 0 3 13 s s 6 6 6 p 4 2 '3 0 3 4 1 The results set forth in Table 4 illustrate the fact that the compounds where R is lower alkyl, e.g. one to four 6 carbon atoms are not herbicides. This 'is. especially so when R is ethyl. Since such compounds are not herbicides'they can be safely applied to growing crops to kill' fungi infesting the crops.

What is claimed is:

l. A process of killing fungi comprising applying to the fungi a fungicidally effective amount of a compound having the formula where R is ethyl or phenyl and R, is lower alkyl.

2. A process according to claim 1 wherein R, has on to four carbon atoms. 3, A process according to claim 1 where R is ethyl.

4. A process according to claim 3 wherein R is ethyl.

5. A process according to claim 3 wherein R, is pheny 6. A process according to claim 5 wherein R, is methyl.

7. A process according to claim 5 wherein R, is ethyl. 8. A process according to claim 2 wherein the compound is applied to soil infested with the fungi.

* III =8 

2. A process according to claim 1 wherein R2 has one to four carbon atoms.
 3. A process according to claim 1 where R1 is ethyl.
 4. A process according to claim 3 wherein R2 is ethyl.
 5. A process according to claim 3 wherein R1 is phenyl.
 6. A process according to claim 5 wherein R2 is methyl.
 7. A process according to claim 5 wherein R2 is ethyl.
 8. A process according to claim 2 wherein the compound is applied to soil infested with the fungi. 